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Title: H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields

Abstract

Roaming mechanisms, involving the brief generation of a neutral atom or molecule that stays in the vicinity before reacting with the remaining atoms of the precursor, are providing valuable insights into previously unexplained chemical reactions. Here in this paper, the mechanistic details and femtosecond time-resolved dynamics of H 3 + formation from a series of alcohols with varying primary carbon chain lengths are obtained through a combination of strong-field laser excitation studies and ab initio molecular dynamics calculations. For small alcohols, four distinct pathways involving hydrogen migration and H 2 roaming prior to H 3 + formation are uncovered. Despite the increased number of hydrogens and possible combinations leading to H 3 + formation, the yield decreases as the carbon chain length increases. The fundamental mechanistic findings presented here explore the formation of H 3 +, the most important ion in interstellar chemistry, through H 2 roaming occurring in ionic species.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [1];  [1];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [1]; ORCiD logo [1];  [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry
  2. Kansas State Univ., Manhattan, KS (United States). J. R. Macdonald Lab., Physics Dept.
  3. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry, and Dept. of Physics and Astronomy
Publication Date:
Research Org.:
Michigan State Univ., East Lansing, MI (United States); Kansas State Univ., Manhattan, KS (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1490277
Grant/Contract Number:  
SC0002325; FG02-86ER13491
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ekanayake, Nagitha, Severt, Travis, Nairat, Muath, Weingartz, Nicholas P., Farris, Benjamin M., Kaderiya, Balram, Feizollah, Peyman, Jochim, Bethany, Ziaee, Farzaneh, Borne, Kurtis, Raju P., Kanaka, Carnes, Kevin D., Rolles, Daniel, Rudenko, Artem, Levine, Benjamin G., Jackson, James E., Ben-Itzhak, Itzik, and Dantus, Marcos. H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields. United States: N. p., 2018. Web. doi:10.1038/s41467-018-07577-0.
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Ekanayake, Nagitha, Severt, Travis, Nairat, Muath, Weingartz, Nicholas P., Farris, Benjamin M., Kaderiya, Balram, Feizollah, Peyman, Jochim, Bethany, Ziaee, Farzaneh, Borne, Kurtis, Raju P., Kanaka, Carnes, Kevin D., Rolles, Daniel, Rudenko, Artem, Levine, Benjamin G., Jackson, James E., Ben-Itzhak, Itzik, & Dantus, Marcos. H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields. United States. doi:10.1038/s41467-018-07577-0.
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Ekanayake, Nagitha, Severt, Travis, Nairat, Muath, Weingartz, Nicholas P., Farris, Benjamin M., Kaderiya, Balram, Feizollah, Peyman, Jochim, Bethany, Ziaee, Farzaneh, Borne, Kurtis, Raju P., Kanaka, Carnes, Kevin D., Rolles, Daniel, Rudenko, Artem, Levine, Benjamin G., Jackson, James E., Ben-Itzhak, Itzik, and Dantus, Marcos. Sat . "H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields". United States. doi:10.1038/s41467-018-07577-0. https://www.osti.gov/servlets/purl/1490277.
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@article{osti_1490277,
title = {H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields},
author = {Ekanayake, Nagitha and Severt, Travis and Nairat, Muath and Weingartz, Nicholas P. and Farris, Benjamin M. and Kaderiya, Balram and Feizollah, Peyman and Jochim, Bethany and Ziaee, Farzaneh and Borne, Kurtis and Raju P., Kanaka and Carnes, Kevin D. and Rolles, Daniel and Rudenko, Artem and Levine, Benjamin G. and Jackson, James E. and Ben-Itzhak, Itzik and Dantus, Marcos},
abstractNote = {Roaming mechanisms, involving the brief generation of a neutral atom or molecule that stays in the vicinity before reacting with the remaining atoms of the precursor, are providing valuable insights into previously unexplained chemical reactions. Here in this paper, the mechanistic details and femtosecond time-resolved dynamics of H3 + formation from a series of alcohols with varying primary carbon chain lengths are obtained through a combination of strong-field laser excitation studies and ab initio molecular dynamics calculations. For small alcohols, four distinct pathways involving hydrogen migration and H2 roaming prior to H3 + formation are uncovered. Despite the increased number of hydrogens and possible combinations leading to H3 + formation, the yield decreases as the carbon chain length increases. The fundamental mechanistic findings presented here explore the formation of H3 +, the most important ion in interstellar chemistry, through H2 roaming occurring in ionic species.},
doi = {10.1038/s41467-018-07577-0},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {12}
}
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DOI:  10.1038/s41467-018-07577-0
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Cited by: 9 works
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Figures / Tables:

Fig. 1 Fig. 1: Primary H3+ formation pathways from methanol (CH3OH) and ethanol (CH3CH2OH). Formation occurs via the neutral H2 roaming mechanism under strong-field laser ionization. In both molecules, the carbon atom attached to the hydroxyl functional group is referred to as the α-carbon and the corresponding hydrogen atoms are referred tomore » as α-hydrogens. In the case of ethanol, the terminal carbon atom and hydrogen atoms are referred to as the β-carbon and the β-hydrogen atoms, respectively« less
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Works referenced in this record:

Generating Efficient Quantum Chemistry Codes for Novel Architectures
journal, November 2012

  • Titov, Alexey V.; Ufimtsev, Ivan S.; Luehr, Nathan
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 1
  • DOI: 10.1021/ct300321a

Real‐time femtosecond probing of ‘‘transition states’’ in chemical reactions
journal, August 1987

  • Dantus, Marcos; Rosker, Mark J.; Zewail, Ahmed H.
  • The Journal of Chemical Physics, Vol. 87, Issue 4, p. 2395-2397
  • DOI: 10.1063/1.453122

Dissociation processes of polyatomic molecules
journal, October 1975

  • Band, Yehuda B.; Freed, Karl F.
  • The Journal of Chemical Physics, Vol. 63, Issue 8
  • DOI: 10.1063/1.431775

Dissociation of methanol by ion-impact: Breakup dynamics, bond rearrangement and kinetic energy release
journal, September 2008

  • De, Sankar; Roy, A.; Rajput, Jyoti
  • International Journal of Mass Spectrometry, Vol. 276, Issue 1
  • DOI: 10.1016/j.ijms.2008.06.021

Chemical Aspects of Astrophysically Observed Extraterrestrial Methanol, Hydrocarbon Derivatives, and Ions
journal, January 2016

  • Olah, George A.; Mathew, Thomas; Prakash, G. K. Surya
  • Journal of the American Chemical Society, Vol. 138, Issue 5
  • DOI: 10.1021/jacs.6b00343

Channel electron multiplier and channelplate efficiencies for detecting positive ions
journal, September 2005

  • Krems, M.; Zirbel, J.; Thomason, M.
  • Review of Scientific Instruments, Vol. 76, Issue 9
  • DOI: 10.1063/1.2052052

Formation of fragment ions (H+, H3+, CH3+) from ethane in intense femtosecond laser fields – from understanding to control
journal, January 2013

  • Schirmel, Nora; Reusch, Nicola; Horsch, Philipp
  • Faraday Discussions, Vol. 163
  • DOI: 10.1039/c3fd20152j

A Theoretical Study on the Photodissociation of Acetone: Insight into the Slow Intersystem Crossing and Exploration of Nonadiabatic Pathways to the Ground State
journal, May 2010

  • Maeda, Satoshi; Ohno, Koichi; Morokuma, Keiji
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 12
  • DOI: 10.1021/jz100551y

An atomic orbital-based formulation of the complete active space self-consistent field method on graphical processing units
journal, June 2015

  • Hohenstein, Edward G.; Luehr, Nathan; Ufimtsev, Ivan S.
  • The Journal of Chemical Physics, Vol. 142, Issue 22
  • DOI: 10.1063/1.4921956

The Roaming Atom: Straying from the Reaction Path in Formaldehyde Decomposition
journal, November 2004

The Formation and Depletion of Molecules in Dense Interstellar Clouds
journal, October 1973

  • Herbst, Eric; Klemperer, William
  • The Astrophysical Journal, Vol. 185
  • DOI: 10.1086/152436

Ab initio molecular dynamics study of cis–trans photoisomerization in ethylene
journal, December 1998

Ab Initio Multiple Spawning Dynamics of Excited Butadiene: Role of Charge Transfer
journal, November 2009

  • Levine, Benjamin G.; Martínez, Todd J.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 46
  • DOI: 10.1021/jp907111u

Evidence of Roaming Dynamics and Multiple Channels for Molecular Elimination in NO 3 Photolysis
journal, July 2010

  • Grubb, Michael P.; Warter, Michelle L.; Suits, Arthur G.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 16
  • DOI: 10.1021/jz1008888

Roaming is the dominant mechanism for molecular products in acetaldehyde photodissociation
journal, August 2008

  • Heazlewood, B. R.; Jordan, M. J. T.; Kable, S. H.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 35
  • DOI: 10.1073/pnas.0802769105

Molpro: a general-purpose quantum chemistry program package: Molpro
journal, July 2011

  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2
  • DOI: 10.1002/wcms.82

Observation of the Infrared Spectrum of H 3 +
journal, August 1980

A comparison of the efficiency and accuracy of the quadratic configuration interaction (QCISD), coupled cluster (CCSD), and Brueckner coupled cluster (BCCD) methods
journal, February 1992

Extension of renormalized coupled-cluster methods including triple excitations to excited electronic states of open-shell molecules
journal, June 2005

  • Włoch, Marta; Gour, Jeffrey R.; Kowalski, Karol
  • The Journal of Chemical Physics, Vol. 122, Issue 21
  • DOI: 10.1063/1.1924596

Nanoscale Multireference Quantum Chemistry: Full Configuration Interaction on Graphical Processing Units
journal, September 2015

  • Fales, B. Scott; Levine, Benjamin G.
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 10
  • DOI: 10.1021/acs.jctc.5b00634

Photodissociation of acetaldehyde as a second example of the roaming mechanism
journal, October 2006

  • Houston, P. L.; Kable, S. H.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 44
  • DOI: 10.1073/pnas.0604441103

Einige Bemerkungen über den Begriff der Säuren und Basen
journal, January 1923

Thermal energy reactions of H+3 and H3O+ with a series of small organic molecules
journal, September 1992

  • Sung Lee, Hack; Drucker, Mark; Adams, Nigel G.
  • International Journal of Mass Spectrometry and Ion Processes, Vol. 117
  • DOI: 10.1016/0168-1176(92)80088-I

The ion detection efficiency of microchannel plates (MCPs)
journal, April 2002

XSEDE: Accelerating Scientific Discovery
journal, September 2014

  • Towns, John; Cockerill, Timothy; Dahan, Maytal
  • Computing in Science & Engineering, Vol. 16, Issue 5
  • DOI: 10.1109/MCSE.2014.80

Hydrogen migration in methanol studied under asymmetric fs laser irradiation
journal, June 2014

Roaming
journal, April 2014

Roaming mediated nonadiabatic dynamics in molecular hydrogen elimination from propane at 157 nm
journal, September 2016

Complex Organic Interstellar Molecules
journal, September 2009

Ejection of triatomic hydrogen molecular ion from methanol in intense laser fields
journal, October 2005

Interstellar Alcohols
journal, July 1995

  • Charnley, S. B.; Kress, M. E.; Tielens, A. G. G. M.
  • The Astrophysical Journal, Vol. 448
  • DOI: 10.1086/175955

Theories and simulations of roaming
journal, January 2017

  • Bowman, Joel M.; Houston, Paul L.
  • Chemical Society Reviews, Vol. 46, Issue 24
  • DOI: 10.1039/C7CS00578D

On the Possible Occurence of H_{3}^{+} in Interstellar Space.
journal, November 1961

  • Martin, D. W.; McDaniel, E. W.; Meeks, M. L.
  • The Astrophysical Journal, Vol. 134
  • DOI: 10.1086/147232

XIX. Further experiments on positive rays
journal, August 1912

  • Thomson, J. J.
  • The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 24, Issue 140
  • DOI: 10.1080/14786440808637325

Coincidence momentum imaging of ultrafast hydrogen migration in methanol and its isotopomers in intense laser fields
journal, May 2006

State‐selected reactive scattering. I. H + 2 +H 2 →H + 3 +H
journal, October 1991

  • Pollard, J. E.; Johnson, L. K.; Lichtin, D. A.
  • The Journal of Chemical Physics, Vol. 95, Issue 7
  • DOI: 10.1063/1.461704

Dynamical, spectroscopic and computational imaging of bond breaking in photodissociation: roaming and role of conical intersections
journal, January 2015

  • Nakamura, Masaaki; Tsai, Po-Yu; Kasai, Toshio
  • Faraday Discussions, Vol. 177
  • DOI: 10.1039/C4FD00174E

The ion chemistry of interstellar clouds
journal, November 1992

Dissociative ionization of ethane with femtosecond pulses of radiation
journal, January 2018

  • Boran, Y.; Gutsev, G. L.; Kolomenskii, A. A.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 51, Issue 3
  • DOI: 10.1088/1361-6455/aa98d4

Roads leading to roam. Role of triple fragmentation and of conical intersections in photochemical reactions: experiments and theory on methyl formate
journal, January 2014

  • Tsai, Po-Yu; Chao, Meng-Hsuan; Kasai, Toshio
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 7
  • DOI: 10.1039/C3CP53792G

Theoretical study of unimolecular decomposition of allene cations
journal, December 2008

  • Mebel, A. M.; Bandrauk, A. D.
  • The Journal of Chemical Physics, Vol. 129, Issue 22
  • DOI: 10.1063/1.3037204

Formation of nascent soot and other condensed-phase materials in flames
journal, January 2011

Ejection dynamics of hydrogen molecular ions from methanol in intense laser fields
journal, June 2006

  • Okino, T.; Furukawa, Y.; Liu, P.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 39, Issue 13
  • DOI: 10.1088/0953-4075/39/13/S24

Coherent vibrations in methanol cation probed by periodic H3+ ejection after double ionization
journal, March 2018

Dissociative recombination of H3+ and some other interstellar ions: a controversy resolved
journal, November 1993

Half‐collision description of final state distributions of the photodissociation of polyatomic molecules
journal, April 1981

  • Band, Yehuda B.; Freed, Karl F.; Kouri, Donald J.
  • The Journal of Chemical Physics, Vol. 74, Issue 8
  • DOI: 10.1063/1.441681

Cold Target Recoil Ion Momentum Spectroscopy: a ‘momentum microscope’ to view atomic collision dynamics
journal, June 2000

Quantum Chemistry on Graphical Processing Units. 3. Analytical Energy Gradients, Geometry Optimization, and First Principles Molecular Dynamics
journal, August 2009

  • Ufimtsev, Ivan S.; Martinez, Todd J.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 10
  • DOI: 10.1021/ct9003004

Dissociative Proton Transfer Reactions of H 3 + , N 2 H + , and H 3 O + with Acyclic, Cyclic, and Aromatic Hydrocarbons and Nitrogen Compounds, and Astrochemical Implications †
journal, October 2002

  • Milligan, Daniel B.; Wilson, Paul F.; Freeman, Colin G.
  • The Journal of Physical Chemistry A, Vol. 106, Issue 42
  • DOI: 10.1021/jp014659i

Detection of H+3 in interstellar space
journal, November 1996

Highly charged ions
journal, September 2001

Velocity dependence of ionization and fragmentation of methane caused by fast-proton impact
journal, February 1994

The Ionization of Hydrogen by Electron Impact as Interpreted by Positive Ray Analysis
journal, July 1925

Efficient ejection of H3+ from hydrocarbon molecules induced by ultrashort intense laser fields
journal, September 2008

  • Hoshina, Kennosuke; Furukawa, Yusuke; Okino, Tomoya
  • The Journal of Chemical Physics, Vol. 129, Issue 10
  • DOI: 10.1063/1.2973588

Implementation of ab initio multiple spawning in the Molpro quantum chemistry package
journal, May 2008

The uniqueness of hydrogen
journal, January 1923

Roaming Radicals
journal, May 2011

Phase dependence of OD+, HOD+, and H3+ ions released from the deuterated dication of methanol under ω/2ω laser field irradiation
journal, April 2015

Efficient computer implementation of the renormalized coupled-cluster methods: The R-CCSD[T], R-CCSD(T), CR-CCSD[T], and CR-CCSD(T) approaches
journal, December 2002

  • Piecuch, Piotr; Kucharski, Stanisław A.; Kowalski, Karol
  • Computer Physics Communications, Vol. 149, Issue 2
  • DOI: 10.1016/S0010-4655(02)00598-2

Rovibrationally Excited Molecules on the Verge of a Triple Breakdown: Molecular and Roaming Mechanisms in the Photodecomposition of Methyl Formate
journal, February 2016

  • Lombardi, Andrea; Palazzetti, Federico; Aquilanti, Vincenzo
  • The Journal of Physical Chemistry A, Vol. 120, Issue 27
  • DOI: 10.1021/acs.jpca.6b00723

Fragmentation dynamics of the methanol dication
journal, September 2008

Fragmentation of CH 4 caused by fast-proton impact
journal, May 1993

The Origin of Primary H+3 Ions in Mass Spectra
journal, September 1996

Mechanisms and time-resolved dynamics for trihydrogen cation (H3 +) formation from organic molecules in strong laser fields
journal, July 2017

Unusual mechanism for H 3 + formation from ethane as obtained by femtosecond laser pulse ionization and quantum chemical calculations
journal, March 2011

  • Kraus, Peter M.; Schwarzer, Martin C.; Schirmel, Nora
  • The Journal of Chemical Physics, Vol. 134, Issue 11
  • DOI: 10.1063/1.3561311

No Straight Path: Roaming in Both Ground- and Excited-State Photolytic Channels of NO3 -> NO + O2
journal, March 2012

Electrophilic reactions at single bonds. XI. Hydrogen-deuterium exchange of molecular hydrogen and deuterium in superacids involving isomeric triatomic (hydrogen, deuterium) (+) ions
journal, July 1973

  • Olah, George A.; Shen, Jacob.; Schlosberg, Richard H.
  • Journal of the American Chemical Society, Vol. 95, Issue 15
  • DOI: 10.1021/ja00796a030

Molecule formation in the interstellar gas
journal, June 1976

Rapid formation of H + 3 from ammonia and methane following 4 MeV proton impact
journal, April 2009

  • Jochim, Bethany; Lueking, Amy; Doshier, Laura
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 42, Issue 9
  • DOI: 10.1088/0953-4075/42/9/091002
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